Pesticidal compositions comprising ethoxylated citric or tartaric acid derivatives as stabilizing surfactants

ABSTRACT

The invention relates to a plant protecting or veterinary or additive composition, containing beside the active ingredient and other usually applied auxiliaries, such as solid and liquid carrier(s), surface active agent(s) and further additive(s), one or more surface active agent(s) of the general formulae (I) ##STR1## or a mixture thereof, wherein R, R 2 , R 3  and R 4  are independently from each other hydrogen atom, an organic or inorganic cation or a group of the general formula --(CH 2  --CH 2  --O) n  R 1 , wherein 
     R 1  is a C 10-20  alkyl group and 
     n is an integer from 4 to 20, with the provisio that from among the substituents R, R 2  and R 3  at least one is a group of the general formula (CH 2  --CH 2  O) n  R 1 .

The invention relates to plant protecting preparations, veterinary preparations and additive preparations admixable with plant protecting and veterinary preparations containing as surface active agents compounds of the formulae (I) ##STR2## The invention also relates to the preparation of such composition. The meaning of the substituents in the formulae (I) and (II) are as follows:

R, R², R³ and R⁴ are independently hydrogen an organic or inorganic cation, or a group of the formula --(CH₂ CH₂ --O)_(n) R¹, wherein

n is an integer from 4 to 20, and

R¹ is a C₁₀₋₂₀ alkyl group.

The inorganic cation is advantageously a sodium potassium, calcium or magnesium cation. The organic cation is advantageously a cation deriving from an amine, such as triethanolamine or diethanolamine.

The surface active agents of the formulae (I) and (II) used in the preparations according to the invention and their use in cosmetic and detergent therapeutical preparations is disclosed in the published Hungarian Patent specification T/40994.

The compounds of the formulae (I) and (II) can be prepared by ethoxylating a fatty alcohol corresponding to R¹ (mean ethyleneoxide number is n), whereafter it is condensed with citric or tartaric acid and finally a salt is formed as required with an alkaline component supplying the suitable cation (published Hungarian Patent Specification T/40994).

We have found that the surface active agents of the formulae (I) and (II) can be advantageously used in plant protecting and veterinary preparations, respectively.

According to the invention from the surface active agents of the formulae (I) and (II) also additive preparations without any active ingredient can be prepared, which can be admixed at the time of application with the plant protecting or veterinary preparation to be applied.

The surface active agents of the formulae (I) and (II) exert in the preparations according to the invention the following positive effects:

they slow down the chemical decomposition of the active ingredient, and thus exert a stabilizing effect;

they influence the formation of the adsorptive layer (build up; structure modification);

they optimize the reological properties of the preparations, and increase the stability of the dispersion;

in some cases they give rise to a liquid crystalline structure, advantageous from the view-point of the dispersion of active ingredient and stability of the preparation;

they exert a wetting, solubilizing, penetration increasing effect;

they modify the transport character (diffusion, etc.), thereby making them suitable for the penetration of capsules;

they increase the chemical and physical compatibility of the active ingredients, etc.; and

from toxicological point of view they are very favourable, they have no poisonous effect and, biologically they are totally decomposable (a biodegradation of 100%).

The preparations according to the invention contain the surface active agents of the formulae (I) and (II) in the following amounts:

    ______________________________________                                         plant protecting preparations                                                                     0.1-10 mass %                                               veterinary preparations                                                                           0.1-10 mass %                                               additive preparations                                                                             0.1-50 mass %                                               ______________________________________                                    

The plant protecting preparations according to the invention may contain as active ingredient some fungicidal, herbicidal, insecticidal, nematocidal, acaricidal or plant growth regulating agents, such as:

Maneb: [manganese-ethylene-bis(dithiocarbamate)-polymer]

Zineb: [zinc-ethylene-bis(dithiocarbamate)-polymer]

Manozeb: [complex of manganese-ethylene-bis(dithiocarbamate-polymer formed with zinc salt]

Metiram: zinc-polyethylene-thiuram-disulfide complex

Propineb: [zinc-propylene-bis(dithiocarbamate)-polymer]

Kaptan: [1,2,3,6-tetrahydro-N-(trichloromethyl-thio)phthalimide]

Procimidon: [N-(3,5-dichlorophenyl)-1,2-dimethyl-cyclo-propane-1,2-dicarboximide]

Kaptafol: N-(1,1,2,2-tetrachloro-ethylthio)-tetrahydrophthalimide

Folpet: N-(trichloro-methyl-thio)-phthalimide

Anilazin: [2,4-dichloro-6-(2-chloroaniline)-1,3,5-triazine]

Flutriafol: (RS)-2,4'-difluoro-α-(1H-1,2,4-triazole-1-yl-methyl)-benzhydryl-alcohol

Diklofluanid: N,N-dimethyl-N'-phenyl-N'-(fluoro-dichloro-methyl-thio)-sulphamide

Triforin: N,N'-bis-(1-formamido-2,2,2-trichloro-ethyl)-piperazine

Vinklozolin: 3-(3,5-dichloro-phenyl)-5-methyl-vinyl-1,3-oxazolidine-2,4-dione

Dodin: dodecyl-guanidine-acetate

Pirazofos: 2-(0,0-diethyl-thiophosphoryl)-5-methyl-6-carbethoxy-pyrazolo-(1,5-a)-pyrimidine

Bupirimat: 2-ethyl-amino-6-methyl-5-n-butyl-4-yl-dimethyl-sulfamate

Fenarimol: α-(2-chloro-phenyl)-α-(4'-chloro-phenyl)-5"-pyrimidyl-methanol

Benomyl: 1-butyl-carbamoyl-benzimidazole-2-methyl-carbamate

Fuberidazol: 2-(2-furyl)-benzimidazole

Thiabendazol: 4-(4-thiazolyl)-1H-benzimidazole

Propiconazol: 1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolane-2-yl-methyl]-1H-1,2,4-triazole

Triadimephon: 1-(4-chloro-phenoxy)-1-(1H-1,2,4-triazole-1-yl)-3,3-dimethyl-2-butanone

Triadimenol: 1-(4-chloro-phenoxy)-1-(1H-1,2,4-triazole-1-yl)-3,3-dimethyl-2-butanol

Bitartanol: β-(1,1'-biphenyl-4-yl-oxy)-β-(1,1-dimethyl-ethyl)-1H-triazole-1-ethanol

Dichlorobutrazol: 1-(2,4-dichloro-phenyl)-4,4-dimethyl-2-(1,2,4-triazole-1-yl)-pentane-3-ol

Thiophanate-methyl: 1,2-bis-(3-methoxy-carbonyl-thioureido)-benzene

Tridemorph: 4-tridecyl-2,6-dimethyl-morpholine

Carbendazim: 2-(methoxy-carbonyl-amino)-benzimidazole

Phenpropiomorph: 4-(3-[4-(1,1-dimethyl-ethyl)-phenyl]-2-methyl)-propyl-2,6-cis-dimethylmorpholine

Metalaxyl: D,L-N-(2,6-dimethyl-phenyl)-N-(2'-methoxyacetyl)-alanine-methyl-ester

Prochlorase: N-propyl-N-[2-(2,4,6-trichloro-phenoxy)-ethyl]-imidazole-1-carboxamide

Permethrin: (±)-cis,transz-3-3(2,2-dichloro-vinyl)-2,2-dimethyl-cyclopropanic acid-3-phenoxy-benzyl-ester

Cypermethrin: 2,2-dimethyl-3-(2,2-dichloro-vinyl)-cyclopropane carboxylic acid-(α-cyano-3-phenoxybenzyl)-ester

Deltamethrin: (1R, 3R)-3-(2,2-dibromo-vinyl)-2,2-dimethyl-cyclopropane carboxylic acid-(S)-α-cyano-m-phenoxy-benzyl-ester

Bifenthrin: (2-methyl)-1,1'-biphenyl(-3-il)methyl-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethyl-cyclopropane-carboxylate

Fempropathrin: α-cyano-3-phenoxybenzyl-2,2,3,3-tetramethyl-cyclopropane-carboxylate

Malathion: 0,0-dimethyl-S-(1,2-dicarbethoxy-ethyl)-dithiophosphate

Chlorphenvinphos: 0,0-diethyl-1-(2,4-dichloro-phenyl)-2-chloro-vinyl-phosphate

Chlorpiriphos: 0,0-diethyl-0-(3,5,6-trichloro-2-pyridyl)-thiophosphate

Dichlorphos: 0,0-dimethyl-2,2-dichloro-vinyl-phosphate

Dimetoate: 0,0-dimethyl-S-(N-methyl-carbamoyl-methyl)-dithiophosphate

Phenitrotion: 0,0-dimethyl-0-(3-methyl-4-nitro-phenyl)-thiophosphate

Aldicarb: 2-methyl-2-methylthio-propionaldehyde-0-methyl-carbamoyl-oxume

Carbaryl: N-methyl-1-naphthyl-carbamate

Diazinon: 0,0-diethyl-0-(2-isopropyl-4-methyl-pyrimidinyl)-thiophosphate

Bensultap: S,S'-[2-(dimethyl-amino)-trimethylene]bis-(benzene-thiosulphonate)

Endosulphane: 1,4,5,6,7,7-hexachloro-bicyclo-(1,1,2)-5-heptane-2,3-bis-(oxymethylene)-sulphite

Phenvalerate: α-cyano-m-phenoxy-benzyl-α-isopropyl-p-chloro-phenyl-acetate

Metidation: 0,0-dimethyl-S-(2-methoxy-1,3,4-thiadiazole-5-(4H)-onyl-(4)-methyl)-dithiophosphate

Metomyl: S-methyl-N-(methyl-carbamoyl-oxy)-thioacetimidate

Mevinphos: 0,0-dimethyl-0-(1-methyl-2-carbomethoxy)-vinyl-phosphate

Trichlorphon: 0,0-dimethyl-1-hydroxy-2,2,2-trichloro-ethyl-phosphonate

Terbuphos: 0,0-diethyl-S-tert-butyl-thiomethyl)-phosphordithioate

Quinalphos: 0,0-diethyl-0-[quinoxalinyl(2)-]thionphosphate

Pyrimiphos-methyl: 0,0-dimethyl-0-(2-diethyl-amino-4-methyl-pyrimidine-6-yl)-thiophosphate

Phosalon: 3-0,0-diethyl-dithiophosphoryl-methyl-6-chloro-benzoxazolone

Chinmix: 1RcisS+1ScisR and 1RtransS+1StransR enantiomer pairs of (RS)-α-cyano-3-phenoxybenzyl(1RS)-cis-trans-3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropane-carboxylate

Transmethrin: 1RtransS and 1StransR enantiomer pairs of (RS)-α-cyano-3-phenoxybenzyl (1RS)cis-trans-3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropane-carboxylate

The plant protecting preparations according to the invention can be formulated in the following forms: emulsion forming preparation (EC): wettable powders (WP); dispersible granulate (WG); suspension concentrate (SC) ULV preparation; concentrated aqueous solution (SL); microemulsion (EW); capsule-suspension (CS).

The veterinary preparations according to the invention can be formulated advantageously in the following forms: injection solutions, solutions suitable for oral dosage, concentrate-preparations, emulsions, suspensions, powders, granulates, pilules, tablets, boles, aerosols, pour-on and spot-on preparations.

The additive preparations according to the invention can be formulated advantageously in the following forms: aqueous solutions (SL), anhydrous concentrates (mixture with other surface active agents and/or with components of other function, e.g. with a diluting component, a solvent, a filling agent.)

In the course of the preparation of compositions according to the invention technologies generally used for the preparation of said formulations can be applied. The preparations according to the invention are containing or can contain beside the surface active agents of the formulae (I) and (II) other generally used additives, such as solid or liquid carriers, surface active agents and other additives.

The surface active agents of the formulae (I) and (II) may be--depending on the meaning of substituents R, R² and R³ --of anionic or nonionic type. The surface active agents of the formula (I) are of anionic type, in which one or two of the substituents R, R² and R³ are a hydrogen atom, or they represent an organic or inorganic cation. Those compounds of the formula (II) are of the anionic type, in which R⁴ represents a hydrogen atom or an organic or inorganic cation.

The solubility of the surface active agents of the formulae (I) and (II) depends on the quality of the cations taking part in the salt formation.

In the course of the preparation of compositions according to the invention the compounds of the formulae (I) and/or (II) can be applied without dilution or diluted, in the last case in the form of aqueous solutions.

In an aqueous medium it is possible even in a relatively low concentration to form solutions of a mean viscosity. One of the advantages of the new tensides is that their solutions are barely foaming.

In the case using the compounds of the formulae (I) and (II) in an aqeuous medium, it is preferable to adjust the pH between 5 and 7, but a more acidic medium (pH 2-5) is also suitable.

(Naturally the pH must be chosen in a way, that it must be tolerable to the active ingredient, too.)

The compounds of the formulae (I) and (II) have very different properties depending on the meaning of R, R¹, R², R³ and n, so they can be applied widely.

In Table I the properties of two, types, which are excellently soluble in water are summarized:

                  TABLE I                                                          ______________________________________                                                       disodium-  sodium                                                              monolaureate-7-                                                                           dilaureate-7-                                                       citrate    citrate                                               ______________________________________                                         Cation          Na           Na                                                EO              7            7 + 7                                             type of ester   mono         di                                                solvent         water        water                                             dry substance   25 ± 1    25 ± 1                                         50° C., 16.sup.h)                                                       water %         75 ± 1    75 ± 1                                         viscosity 20° C. mP                                                                     about 30     about 700                                         pH (1% of active                                                                               6.5 ± 0.3 6.5 ± 0.3                                      ingredient in water)                                                           surface tension at 20° C.                                               (dyn/cm)                                                                       0.25 g/l active 33.2         31.5                                              ingredient                                                                     1.0 g/l active  32.3         31.0                                              ingredient                                                                     ______________________________________                                    

In Table II some compounds of the formulae (I) and (II) are described suitable for application in the preparations according to the invention.

                                      TABLE II                                     __________________________________________________________________________           Ester                       Surface                                                                               Solvent,                                    M = mono                                                                             Type                  active agent                                                                          carrier                               Component                                                                            D = di                                                                               acid = 8                                                                            R.sub.1   Starting                                                                              quantity                                                                              quantity                              (code)                                                                               T = tri                                                                              salt alkyl                                                                              n     acid   mass % mass %                                __________________________________________________________________________     A     M     H    lauryl                                                                              7    citric acid                                                                           100    --                                                     C.sub.12                                                      B     M     Na   lauryl                                                                              8    citric acid                                                                            25    water                                                  C.sub.12                                                      C     M     Na   lauryl                                                                             20    citric acid                                                                           100    --                                                     C.sub.12                                                      D     M     TEA  lauryl                                                                             10    citric acid                                                                           100    --                                                     C.sub.12                                                      E     M     TEA  lauryl                                                                              4    citric acid                                                                            60    Vessalon                                               C.sub.12                                                      F     D     H    C.sub.16                                                                            7 + 7                                                                               citric acid                                                                           100    --                                    G     D     TEA  C.sub.14                                                                            4 + 4                                                                               citric acid                                                                           100    --                                    H     D     TEA  C.sub.18                                                                            6 + 6                                                                               citric acid                                                                            80    xylene                                I     D     Ca   C.sub.12                                                                            7 +  7                                                                              citric acid                                                                            70    butyl diglycol                        J     T     --   C.sub.12                                                                            6 + 6 + 6                                                                           citric acid                                                                           100    --                                    K     M     H    C.sub.12                                                                            6    tartaric acid                                                                         100    --                                    M     D     --   C.sub.12                                                                            5 + 5                                                                               tartaric acid                                                                         100    --                                    N     D     --   C.sub.10                                                                            8 + 8                                                                               tartaric acid                                                                         100    --                                    P     D     --   C.sub.12                                                                            7 + 7                                                                               tartaric acid                                                                          70    xylene                                R     M     Na   C.sub.12                                                                            6    citric acid                                                                            80    DMA                                   O     M     Na   C.sub.12                                                                            6    tartaric acid                                                                          25    water                                 S     D     Na   C.sub.12                                                                            6 + 6                                                                               citric acid                                                                            25    water                                 T     D     Na   C.sub.12                                                                            6 + 6                                                                               citric acid                                                                           100    --                                    X     M     K    C.sub.12                                                                            9 + 9                                                                               tartaric acid                                                                          40    water                                 Y     T     --   C.sub.12                                                                            4 + 4 + 4                                                                           citric acid                                                                            50    Vessalon                              Z     M     Ca   C.sub.12                                                                            7    citric acid                                                                           100    --                                    V     D     TEA  C.sub.12                                                                            5 + 5                                                                               citric acid                                                                           100    --                                    W     D     MEA  C.sub.12                                                                            5 + 5                                                                               citric acid                                                                            50    water                                 __________________________________________________________________________

The surface activity of compounds of the formulae (I) and (II) is excellent, that is they decrease suitably the water/air interfacial tension even in a low concentration.

This is illustrated in Table III.

                  TABLE III                                                        ______________________________________                                                          Surface tension dyn/cm                                                         0.25 g/l                                                                              1 g/l                                                  ______________________________________                                         Compound of the                                                                formula (I)                                                                    code                                                                           S                  1.5      31.0                                               B                  33.2     32.3                                               O                  34.0     33.6                                               Sodium-dodecyl-    41.2     34.2                                               benzene-sulphonate                                                             Sodium-lauryl-ether-                                                                              35.0     31.8                                               sulphate (EO:2)                                                                ______________________________________                                    

The preparations according to the invention are illustrated by the following examples, without any limitation as to the scope of invention.

1. Emulsion forming agents

(In the following preparations the components according to the invention (A, F, K) increase the chemical stability of the active ingredients.)

    ______________________________________                                         a.)    Dichlorvos (96%)   20.85 mass %                                                Component A        2 mass %                                                    Emulson AG/CAL     3 mass %                                                    Emulson AG/EL      4 mass %                                                    Xylene             ad 100 mass %                                        where Emulson AG/CAL = calcium-dodecyl-                                        benzene-sulphonate (a 60% active ingredient                                    solution).                                                                     b.)    Cypermethrin (90%) 11.1 mass %                                                 Component F        1.5 mass %                                                  Emulson AG/CAL     2.5 mass %                                                  Emulson AG/COH     2.5 mass %                                                  Solvesso 150       ad 100 mass %                                        where Emulsion AG/COH = ethoxylated EO:25                                      hydrogenated (saturated) castor oil derivative.                                Solvesso 150 = aromatic solvent.                                               c.)    Phenmedipham (97%) 16.1 mass %                                                 Component K        2.0 mass %                                                  Emulsogen AG/CAL   5.0 mass %                                                  Emulson AG/2B      4.0 mass %                                                  Emulson AG/7B      9.0 mass %                                                  Isophoron          ad 100 mass %                                        where                                                                          Emulson AG/2B = ethoxylated nonylphenol, EO:2                                  Emulson AG/98 = ethoxylated nonylphenol, EO:9                                  ______________________________________                                    

2. Emulsion forming agents (EC)

(In the following preparations the components according to the invention (G, Z, H, J, P, M) possess emulsifying activity.)

    ______________________________________                                         a.) Metolachcor (96%)                                                                              75 mass %      75 mass %                                       Component G     6 mass %       3 mass %                                        Emulson AG/CAL  --             2 mass %                                        Emulson AG/PE   4 mass %       --                                              Emulson AG/EL   --             5 mass %                                        Xylene                         ad 100 mass %                               where Emulson AG/PE = an EO + PrO condensate                                   b.) Cypermethrin (90%)                                                                             11. mass %     20.8 mass %                                     Component Z     5 mass %       5 mass %                                        Emulson AG/CAL  1 mass %       2.5 mass %                                      Emulson AG/EL   2 mass %       2.5 mass %                                      Solvesso 150    --             ad 100 mass %                                   Xylene          ad 100 mass %  --                                              Cyclohexanone   --             10 mass %                                   c.) Quinalphos (in  50 mass %      50 mass %                                       50% xylene)                                                                    Component H     6 mass %       4 mass %                                        Component J     2 mass %       2 mass %                                        Component P     2 mass %       --                                              Component M     --             4 mass %                                        Xylene          ad 100 mass %  ad 100 mass %                               ______________________________________                                    

3. Aqueous solutions (SL)

Foliage wetting increasing activity (promotion of biological activity)

    ______________________________________                                         MCPA K - salt (97%)                                                                               412    g/l      --                                          Dichloroprop K-salt (95%)                                                                         --              526  g/l                                    Component B        20     g/l      --                                          Component S        --              25   g/l                                    Water              ad 1   liter                                                ______________________________________                                    

4. Water soluble powder concentrate (SP)

Wetting agent, drop-spreading increasing effect.

    ______________________________________                                         Cartapchloride (95%)                                                                               42.1    mass %                                             Component M         3       mass %                                             Powdered sugar      ad 100  mass %.                                            ______________________________________                                    

Component M advantageously moderates the agglomerating tendency of the preparation formed with water soluble sugar due to its hygroscopic property, that is it ensures better storage.

5. Sprayable powders (WP)

    ______________________________________                                         Wetting agent                                                                  ______________________________________                                         Benomyl (95%)                                                                             52.6 mass %                                                                               --       --     --                                       Carbendazim (97%)                                                                         --          51.6    --     --                                       Folpet (93%)                                                                              --         --       50     --                                       Copperoxychloride                                                                         --         --       30     --                                       (50% copper)                                                                   Permetrin (95%)                                                                           --         --       --     26                                       Ultrasil VN 3                                                                              5         5        5      20                                       Calciumcarbonate                                                                          ad 100     --       --     --                                       Kaolin     --         ad 100%  ad 100%                                                                               ad 100%                                  Component E                                                                                3.5       2        --     --                                       Component Y                                                                               --         2        3       3                                       Borresperse 3 A                                                                            3.5       3        5       4                                       where Borresperse 3 A = sodium-lignin-sulphonate                               ______________________________________                                    

6. Suspension concentrates (SC)

    __________________________________________________________________________               mass %                                                               __________________________________________________________________________     Flutriafol (98%)                                                                         25.5 --   --   --   --   --   --                                     Carbendazim (96%)                                                                        --   20.9 --   --   --   --   --                                     Carbofuran (93%)                                                                         --   --   43   --   --   --   --                                     Atrazine (97%)                                                                           --   --   --    51.5                                                                               --   --   --                                     Isoproturon (96%)                                                                        --   --   --   --   47.5 --   --                                     Chloridazon (92%)                                                                        --   --   --   --   --   38.9 --                                     Copperoxychloride                                                                        --   --   --   --   --   --   6                                      (50% copper)                                                                   White oil --   20   8    --   --   --   --                                     Component W                                                                              0.5  1.5  --   0.4  0.4  --   --                                     Component O                                                                              0.5  --   --   --   --   0.8  --                                     Component S                                                                              --   --   1    --   0.2  --    1                                     Propyleneglycol                                                                          5    6    6    6    6    6    6                                      Emulson AG/1314                                                                          0.5  0.3  0.5  --   0.5  2    0.5                                    Emulson AG/6130                                                                          1.0  0.75 0.9  1    0.8  --   1.5                                    Emulson AG/2527                                                                          --   1.2  0.9  --   --   0.5  --                                     Madeol AG/2376                                                                           0.5  0.5  0.2  0.2  0.2  0.15 0.2                                    Product 0028                                                                             0.5  0.4  0.5  0.5  0.5  --   0.5                                    Water     ad 100%                                                                             ad 100%                                                                             ad 100%                                                                             ad 100%                                                                             ad 100%                                                                             ad 100%                                                                             ad 100%                                __________________________________________________________________________

where

Madeol AG/2376=xanthan gum+silicic acid

Product 0028=silicon oil emulsion (30%) antifoaming agent

Emulson AG/1314=ethoxylated bisphenol (EO: 13)

Emulson AG/2527=ethoxylated castor oil (EO: 25)

Emulson AG/6130=triethanolamine salt of ethoxylated and phosphatized bisphenol (mixture of mono- and diphosphate, ethoxylation: 13 EO)

7. Wettable powders (WS)

    ______________________________________                                                          mass %                                                        ______________________________________                                         Carbendazim (96%) 52.1      --     --                                          Folpet (93%)      --        53.8   --                                          Copper oxyquinolate (95%)                                                                        --        --     52.6                                        Ultrasil VN 3     5         5      5                                           Mowinol 4/88      8         8      8                                           Madeol AG/OR 95   2.5       3      3.5                                         Component T       3         2.5    3.5                                         Irgalite-blue     1         1      0.8                                         Kaolin             ad 100                                                      ______________________________________                                    

where

Mowinol 4/88=polyvinyl-alcohol (Hoechst)

Irgalite-blue=colouring agent

8. Suspension dressing agents (FS)

    ______________________________________                                                          mass %                                                        ______________________________________                                         Carbendazim (96%) 26.1      --     --                                          Flutriafol (98%)  --        12.8   --                                          Copper oxyquinolate (95%)                                                                        --        --     21.1                                        Ethyleneglycole   7         7      7                                           Vinavil EVA 06 T  18        18     18                                          Component K       1         --     0.3                                         Component S       --        0.8    0.3                                         Emulson AG/1314   0.2       0.5    --                                          Emulson AG/PE     0.3       1.2    --                                          Emulson AG/6130   0.5       --     1.5                                         Madeol AG/2376    0.1       0.2    --                                          Basasol ROT 76 L  0.5       0.5    0.8                                         Silison SRE       0.7       0.7    0.5                                         Water              ad 100                                                      ______________________________________                                    

where

Vinavil EVA 06 T=a film forming polymer polyvinylacetate derivative (Montedison)

Basasol ROT 76 L=a coloring component (BASF)

Silison SRE=an antifoaming agent in a silicone oil emulsion of 30% (Wacker).

9. Microemulsions (EW)

(a good stability between -5° C. and 54° C.)

    ______________________________________                                                         mass %                                                         ______________________________________                                         a.)   Cypermetrin (90%)                                                                            4.5        4.5  --                                               Permetrin (95%)                                                                              --         --   10.5                                             PBO (90%)     --         15   --                                               Component B   3.0        --   5.0                                              Component O   2.0        1.0  --                                               Component S   --         4.0  --                                               Emulson AG/1314                                                                              12         15   14                                               Emulson AG/0600                                                                              3          3    6                                          Water             ad 100                                                       ______________________________________                                    

where

Emulson AG/0600=Emulson AG/CAL (calcium-dodecyl-benzosulphonate)

PBO=piperonyl-butoxyde

    ______________________________________                                                         mass %                                                         ______________________________________                                         b.) Cypermetrin-isomer (g/l)                                                   1RcisS + 1ScisR                                                                    20                20     --     --                                         1RtransS + 1StransR                                                                30                30     50     50                                             PBO               --     100    --  100                                        Ethyleneglycol    90     --     90  --                                         Propyleneglycol   --     90     --  90                                         Butanol           50     --     40  30                                         Ethanol           --     40     --  --                                         Component B       60     50     40  60                                         Component O       --     10     10  90                                         Component S       --      5     10  --                                         Emulson AG/1314   100    70     50  70                                         Emulson AG/0600   60     40     50  60                                     Water             ad 1000 ml                                                   ______________________________________                                                        mass %                                                          ______________________________________                                         c.) Quinalphos       250    250  200  --   200                                     Cypermetrin isomer                                                         1RcisS + 1ScisR                                                                    --               --     20   --   --                                       1RtransS + 1StransR                                                                --               --     30   50   50                                           Tetrametrin      --     --   --    5   --                                      PBO              --     --   --   100  --                                      Butly-hydroxytoluene                                                                            --     --   10   10   10                                      Solvesso         200    --   10   --   --                                      Butanol          70     200  50   10   30                                      Component B      50     --   10   --   25                                      Component O      70     --   --   100  --                                      Component S      --     100  30   --   40                                      Component H      --      50  --   20   --                                      Component I      --      10  --   --   30                                      Component M      --     --   50   --   15                                      Emulson AG/1314  40     --   10   50   --                                  Water            ad 1000 ml                                                    ______________________________________                                    

10. Granulates dispersable in water (WG)

(promoting quick wetting)

    ______________________________________                                         Carbendazim (96%)                                                                              78.1 mass %                                                                               --                                                  Atrazine (97%)  --         77.3 mass %                                         Component W     3 mass %   --                                                  Component B     13         4.5 mass %                                          Emulson AG/0240 0.7 mass % 0.5 mass %                                          Madeol AG/OR95  5 mass %   5 mass %                                            Ultrasil VN 3   5 mass %   5 mass %                                            Kaolin          ad 100%                                                        ______________________________________                                    

Where Emulson AG/0240=ethoxylated-bisphenol (EO: 24)

In the course of the preparation of the powderous mixtures consisting of the component above--after fine grinding--in the form of an aqueous solution the suitable quantity of the surface active ingredient according to the invention is sprayed in a granulating mixer (plate granulator).

11. Ultra ULV preparations

(Drop spreading and adhesion improving, active ingredient stabilizing, viscosity adjusting effect)

    ______________________________________                                         Cypermethrin (90%)                                                                            11.1 mass %  --                                                 Phosalome (95%)                                                                               --           26.3 mass %                                        Solvesso 200   25.0 mass %  35.0 mass %                                        Component I    2.0 mass %   2.0 mass %                                         Sunflower oil  ad 100 mass %                                                                               ad 100 mass %                                      ______________________________________                                    

12. Microcapsule

(Control of the active ingredient release, influencing the capsule-preparation)

    ______________________________________                                                              mass %                                                    ______________________________________                                         a.)   Transmetrin          12.62                                                     Tetrametrin          1.24                                                      PBO                  86.14                                                     Poly-phenylisocyanate (31%)                                                                         3.0                                                       Component I          1.0                                                       Water                32.9                                                      aqueous diluted-1,6-hexametylene-                                                                   3.0                                                       diamine solution (1,6-HMD aqueous                                              12.4% solution)                                                                Ethyleneglycol       15.7                                                      Component M          1.0                                                       CaCl.sub.2           3.0                                                 b.)   Permetrin            28.6                                                      Aromatol             21.5                                                      Poly-phenylisocyanate                                                                               3.5                                                       Component I          1.1                                                       Water                40.8                                                      HMD-diluted          3.5                                                       CaCl.sub.2           1.1                                                 c.)   Permetrin            29.0                                                      Solvesso 100         14.6                                                      Component I          1.0                                                       Water                35.6                                                      HMD-diluted          3.0                                                       CaCl.sub.2           5.0                                                       NaCl                 1.0                                                       Component M          1.0                                                 d.)   Cypermetrin:Aromatol 1:1                                                                            47.3                                                      Poly-phenylisocyanate                                                                               3.3                                                       Component I          1.0                                                       HMD-diluted          3.3                                                       Ethyleneglycol       4.9                                                       Water                38.8                                                      CaCl.sub.2           0.6                                                       Component P          0.8                                                 e.)   Cypermetrin:Aromatol 20:15                                                                          38.6                                                      Poly-phenylisocyanate                                                                               2.7                                                       Component I          0.9                                                       Water                31.6                                                      HMD-diluted          2.7                                                       Ethyleneglycol       23.0                                                      CaCl.sub.2           0.5                                                 f.)   Cypermetrin:Aromatol 20:15                                                                          48.0                                                      Poly-phenylisocyanate                                                                               3.4                                                       Component I          1.1                                                       Water                39.5                                                      HMD-diluted          3.4                                                       Ethyleneglycol       2.4                                                       CaCl.sub.2           0.6                                                       Component N          1.2                                                 g.)   Transmetrin-Solvesso 100 10:35                                                                      37.8                                                      Poly-phenylisocyanate                                                                               2.9                                                       Component I          1.6                                                       Water                30.8                                                      HMD-diluted          2.8                                                       Ethyleneglycol       8.1                                                       CaCl.sub.2           12.2                                                      NaCl                 3.3                                                       Component M          0.8                                                 h.)   Transmetrin:Solvesso 100:Xylene                                                                     49.3                                                      10:16:5                                                                        Poly-phenylisocyanate                                                                               3.4                                                       Component I          1.1                                                       Water                40.0                                                      HMD-diluted          3.4                                                       CaCl.sub.2           2.8                                                 i.)   Ekalux 50            38.3                                                      Poly-phenylisocyanate                                                                               3.4                                                       Water                40.0                                                      HMD-diluted          3.4                                                       CaCl.sub.2           2.8                                                 j.)   EPTC                 36.3                                                      Poly-penylisocyanate 2.5                                                       Component I          1.6                                                       Water                29.5                                                      HMD-diluted          3.1                                                       NaCl                 1.6                                                       CaCl.sub.2           3.1                                                       Component M          0.8                                                 k.)   Permetrin-Aromatol (20:15)                                                                          47.5                                                      Poly-phenylisocyanate                                                                               3.2                                                       Component I          1.0                                                       Water                38.1                                                      HMD-diluted          3.2                                                       CaCl.sub.2           5.0                                                       NaCl                 1.0                                                       Component N          1.0                                                 ______________________________________                                    

The microcapsules above were prepared by the following steps:

a.) the active ingredient and the poly-phenylisocyanate were kneaded to a homogenous phase;

b.) the surface active agent and the water were mixed to one phase;

c.) into the aqueous phase (b) the oily phase (a) was poured slowly, thereafter by turaxing slowly while cooling with water an emulsion was formed;

d.) to the emulsion the diluted HMD solution was added drop-by-drop, whereafter while cooling with water the mixture was turaxed;

e.) if necessary to the finished formulation ethyleneglycol was added and the suitable quantities of CaCl₂ and NaCl respectively, were added to adjust the viscosity.

13. Preparation for bathing animals

    ______________________________________                                         Chinmix              250     g/l                                               Component A          70      g/l                                               Xylene               ad 1000 ml                                                ______________________________________                                    

By mixing the mixture above in a ratio of 1:2-1:20 with phenolfree kreoline and diluting the same with a 500-2000 fold quantity of water a good stabilized emulsion for bathing animals is obtained.

Kreolin=mixture of coal oil, Na-iktiol, sodium hydroxide and canifol

14. Additive preparation containing no active ingredient

    ______________________________________                                         a.  Component X                                                                    Potassium-mono-laurate-ethoxy(9)-tartarate                                                              40 mass %                                             Water                    60 mass %                                         b.  Component B                                                                    Sodium-mono-laurate-ethoxy(8)-citrate                                                                   25 mass %                                             Water                    75 mass %                                         ______________________________________                                    

15. Preparation of tankmixtures

Tankmixtures of the following compositions were prepared in a way, that the combination of a plant protecting agent and/or an artificial chemical fertilizer (from time to time in a prediluted form) is added to the additive preparation.

    ______________________________________                                                        mass %                                                          ______________________________________                                         Component X   2.0         --     1.5                                           Component B   --          3.0    1.5                                           Fundazol 50 WP                                                                               1.0         --     --                                            Olitref EC    --          1.2    --                                            Dithiane M-45 1.0         --     0.7                                           Carbamide     --          15.0   --                                            Sequestren 138 Fe                                                                            --          --     1.0                                           Water            ad 100%                                                       ______________________________________                                     

What we claim is:
 1. A plant protecting composition, containing an active ingredient which is 0.1 to 10% by weight of a fungicide, herbicide, insecticide, nematocide, acaricide, and optionally a solid or liquid carrier, and at least one surface active agent of the formulae (I) ##STR3## or a mixture thereof, wherein R, R², R³ and R⁴ are independently from each other hydrogen, an organic or inorganic cation or a group of the formula --(CH₂ --CH₂ --O)_(n) R¹, whereinR¹ is a C₁₀₋₂₀ alkyl group and n is an integer from 4 to 20, provided that at least one of R, R² and R³ is a group of the formula (CH₂ --CH₂ O)_(n) R¹, in an amount effective to stabilize said plant-protecting active ingredient.
 2. A plant protecting composition according to claim 1, formulated in the form of emulsion forming preparation (EC), sprayable powder (WP), dispersable granulate (WG), suspension concentrate (SC), ULV preparation, concentrated aqueous solution (SL), microemulsion (ES) or, capsule suspension (CS).
 3. A veterinary, preparation, containing 0.1 to 10% by weight of a veterinary effective active ingredient which is a fungicide, insecticide, nematocide, or acaricide and a solid or liquid carrier, suitable for use in veterinary therapy, and 0.1-10 mass % of at least one surface active agent of the formulae (I) ##STR4## or a mixture thereof in which R, R², R³ and R⁴ are independently from each other hydrogen, an organic or inorganic cation, or a group of the formula (CH₂ --CH₂ O)_(n) R¹, R¹ is a C₁₀₋₂₀ alkyl group, n is an integer from 4 to 20, provided that at least one of R, R² and R³ is a group of the formula (CH₂ --CH₂ O)_(n) R¹.
 4. The veterinary preparation defined in claim 3 comprising 250 g of Chinmix as the veterinary effective active ingredient; 70 g of the surface active agent of the Formula (I) which is a monoester of citric acid wherein the esterifying moiety has the following formula:

    --(CH.sub.2 --CH.sub.2 O).sub.7 --(CH.sub.2).sub.11 --CH.sub.3

per liter of xylene as the liquid carrier.
 5. A method of slowing down decomposition of a plant-protecting composition containing as a plant-protecting active ingredient, 0.1 to 10% by weight of a fungicide, herbicide, insecticide, nematocide, acaricide, or plant growth regulating agent, while at the same time exerting a wetting, solubilizing, or penetration-enhancing effect, which comprises the step of stabilizing said fungicide, herbicide, insecticide, nematocide, acaricide, or plant growth regulating agent, with a compound of the Formula (I) ##STR5## R¹, R², R³ and R⁴ are independently from each other, hydrogen, an organic or inorganic cation, or a group of the formula --(CH₂ --CH₂ O)_(n) R¹, whereinR¹ is a C₁₀ to C₂₀ alkyl group, and n is an integer from 4 to 20, provided that at least one of R, R², and R³ is a group of the formula --(CH₂ --CH₂ O)--_(n) R¹, in an amount effective to stabilize said plant-protecting active ingredient.
 6. A method of slowing down decomposition of a veterinary composition containing as a veterinary active ingredient, 0.1 to 10% by weight of a fungicide, insecticide, nematocide, or acaricide, while at the same time exerting a wetting, solubilizing, or penetration-enhancing effect, which comprises the step of stabilizing said fungicide, insecticide, nematocide, or acaricide, with a compound of the Formula (I) ##STR6## R¹, R², R³ and R⁴ are independently from each other, hydrogen, an organic or inorganic cation, or a group of the formula --(CH₂ --CH₂ O)_(n) R¹, whereinR¹ is a C₁₀ to C₂₀ alkyl group, and n is an integer from 4 to 20, provided that at least one of R, R², and R³ is a group of the formula --(CH₂ --CH₂ O)_(n) R¹, in an amount effective to stabilize said veterinary active ingredient.
 7. The method of slowing down decomposition of a veterinary composition defined in claim 5 wherein the active ingredient is an insecticide selected from the group consisting of permethrin, cypermethrin, deltamethrin, bifenthrin, fenpropathrin, chinmix and transmethrin. 